S-(ethylxanthoyl) o, o-di(4-nitrophenyl) dithiophosphate



Patented Feb. 9, 1954 S (ETHYLXANTHOYL) '0,0-DI 4-NITRO- PHENYL) DITHIOPHOSPHATE Henry Tolkmith, Midland, Mich., assignor to The Dow Chemical Company, Midland, Mich., a

corporation of Delaware No Drawing. Application April 21, 1953, Serial No. 350,240

1 This invention is directed to S-(ethylxanthoyl) 0,0-di(4-nitrophenyl) dithiophosphate of the formula This compound is a viscous oil, somewhat soluble in many organic solvents and substantially insoluble in water. It is of value as an intermediate for the preparation of more complex phosphorus derivatives and as a. toxic constituent of parasiticide compositions.

The new compound may be prepared by reacting two molecular proportions of 4-nitr0pheno1 with one molecular proportion of S-(ethylxanthoyl) dithiophosphoric dichloride of the formula in an inert organic solvent such as benzene or diethyl ether. The reaction is carried out in the presence of a hydrogen chloride acceptor such as pyridine.

In carrying out the reaction, a mixture of the 4-nitrophenol, pyridine and solvent is added with stirring to the S-(ethylxanthoyl)dithiophosphoric dichloride and the resulting dispersion heated for a period of time at a temperature of from 35 to 80 C. In practice, it is sometimes convenient to operate at the boiling temperature of the reaction mixture and under reflux. Temperatures substantially in excess of 80 C. for any appreciable period of time should be avoided, as the desired product has a tendency to decompose at such temperature. Upon completion of the reaction, the mixture may be filtered and filtrate 1 Claim. (Cl. 260-455) distilled under reduced pressure at temperatures gradually increasing to a temperature of 80 C. to separate low boiling constituents and to obtain as a residue the desired S-(ethylxanthoyl) 0,0-dii-nitrophenyl) dithiophosphate.

The S-(ethylxanthoyl) dithiophosphoric dichloride employed as a starting material in the above-described methods may be prepared by reacting one molecular proportion of sodium ethylxanthate with at least two molecular proportions of phosphorus thiochloride in an inert organic solvent such as benzene. In carrying out the reaction, the reactants are dispersed in the solvent and the resulting mixture heated for a period of time at a temperature of from to 80 C. To avoid decomposition, temperatures substantially in excess of 80 C. for any appreciable period of time should not be employed. Upon completion of the reaction, the mixture may be filtered and the filtrate concentrated by distillation under reduced pressure to a temperature up to C. to obtain as a residue the desired S-(ethylxanthoyl) dithiophosphoric dichloride. This compound is a viscous oil having a density of 1.451 at 21 C. The latter compound and described method for its preparation are disclosed in my copending application Serial No. 203,768.

In a representative preparation, 17.5 grams (0.222 mole) of pyridine and 27.5 grams (0.198 mole) of i-nitrophenol, were dispersed in 200 milliliters of diethyl ether and the resulting mixture added with stirring to 25 grams (0.098 mole) of S-(ethyixanthoyl) dithiophosphoric dichloride dispersed in 200 milliliters of diethyl ether. The reaction mixture was thereafter heated for 10 hours at the boiling temperature and under reflux. The mixture was then filtered and the filtrate concentrated by distillation under reduced pressure to a temperature up to 50 C. to obtain as a residue an S-(ethylxanthoyl) 0,0-di(4- nitrophenyl) dithiophosphate product. The latter is a viscous oil having a density of 1.4110 at 20 C.

The new S-(ethylxanthoyl) 0,0-di(4-nitrophenyl) dithiophosphate product is efiective as a parasiticide and adapted to be employed for the control of a wide range of agricultural and household pests such as flies, mites, aphids, 'beetles and cockroaches and Southern army Worms. For such use, the compound may be dispersed on an inert finely divided solid and employed as a dust. Also, such mixtures may be dispersed in water with the aid of a dispersing and wetting agent and the resulting aqueous suspensions employed as sprays. In other procedures, the new product may be employed in oils, as a constituent in oilin-water emulsions, or in water dispersion with or without the addition of emulsifying, wetting or dispersing agents. Suitable concentrations of the toxicant in dusts are in the order of from about 0.1 to 10 percent by weight of the dust and in liquid suspensions from about 0.1 to 3 pounds per gallons of the spray mixture. In illustrative operations against representative plant pests, 100 percent kills of two-spotted spider mites, bean aphids, Mexican bean beetles and Southern army worms were obtained with aqueous spray compositions containing 0.06, 1.0, 0.25 and 1.5 pounds, respectively, of the toxic dithiophosphate per 100 gallons of spray mixture.

This is a continuation in part of my eopending application Serial No. 203,770, filed December 30. 1950.

I claim:

53 ethylxanthoyl) thiophosphate.

0,0-di(4-nitrophenyl) di- HENRY TOLKMITH.

No references cited. 

